CN102181044A - Novel diamino-alcohol compounds, their manufacture and use in epoxy resins - Google Patents

Novel diamino-alcohol compounds, their manufacture and use in epoxy resins Download PDF

Info

Publication number
CN102181044A
CN102181044A CN201010618068.8A CN201010618068A CN102181044A CN 102181044 A CN102181044 A CN 102181044A CN 201010618068 A CN201010618068 A CN 201010618068A CN 102181044 A CN102181044 A CN 102181044A
Authority
CN
China
Prior art keywords
epoxy
resins
alkyl
hydrogen
resin system
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201010618068.8A
Other languages
Chinese (zh)
Other versions
CN102181044B (en
Inventor
A·A·皮拉
I·汤姆林森
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Angus Chemical Co
Original Assignee
Angus Chemical Co
Dow Global Technologies LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Angus Chemical Co, Dow Global Technologies LLC filed Critical Angus Chemical Co
Publication of CN102181044A publication Critical patent/CN102181044A/en
Application granted granted Critical
Publication of CN102181044B publication Critical patent/CN102181044B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/64—Amino alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Epoxy Resins (AREA)

Abstract

A new class of compounds, namely diamino alcohols, is described, along with a process for their production and their use as hardeners, or curing agents, for epoxy resin systems, some of which have high glass transition temperatures, Tgs, such as greater than about 120 DEG C.

Description

Novel diamino alcohol compound, its manufacture method and the application in Resins, epoxy
Invention field
The present invention relates to the new compound of a class, i.e. diamino alcohol, its production method, with and have application in the Resins, epoxy of high glass-transition temperature (Tg) in preparation.
Technical background
The known character that neutralization can be provided in coating, inorganic slurry and the epoxy preparation, disperse and harden that simple amine compound is added.The manufacture method of simple amine compound is seen and is set forth in many documents, is known in the art, and when target was the preparation primary amine, preferred path often related to intermediate nitroalcohol compound.
The method of making intermediate nitroalcohol compound is known, the normally nitro aldolisation between nitro alkane and the aldehyde (Henry (Henry) reaction).Sometimes can be with reference to relating to series connection Michael's (Michael) addition and nitro alkane and α, the preparation process of the dinitrobenzene alcohol of the Henle reaction of beta-unsaturated aldehyde.For example, referring to " secondary dinitrobenzene alcohol (Secondary dinitro alcohols) ", Smith, Curtis W. (Shell Development Co.), 1949 and No. the 2475996th, United States Patent (USP), these document descriptions nitroalcohol 2,5,6-trimethylammonium-2, the manufacturing of 6-dinitrobenzene-3-enanthol.Also prepare this nitroalcohol as intermediate to make vasoactive phthalein enzyme inhibitors, as Janak Singh etc., effective asymmetric synthesis of vasoactive phthalein enzyme inhibitors BMS-189921 (Efficient Asymmetric Synthesis of the Vasopeptidase Inhibitor BMS-189921), Org.Lett. (2003), 5,17, discuss among the 3155-3158.In addition, David St.Clair Black etc., Australian Journal of Chemistry has described nitroalcohol compound 2 in 1976,29 (11), 2511, the manufacturing of 6-dinitrobenzene-5-phenyl-heptan-3-alcohol.As everyone knows, can be by at appropriate catalyst (for example (Raney) nickel or platinum base or palladium-based catalyst (Pt of element form or oxide form or Pd in Ruan, have or do not have carrier such as carbon)) go up and carry out hydrogenation with hydrogen, easily the nitroalcohol compound is converted into amino alcohol compound.Those of ordinary skills also understand, and other reductive agents that the nitro alkane can be reduced into primary amine comprise metal/acid combination (as iron/acetate) and aluminum hydride.Preferred reductive agent comprises hydrogen and following any catalyzer: Raney nickel, platinum or palladium.
On the other hand, this area does not propose diamino alcohol compound and application thereof at present as yet.
Known amine and amino alcohol are stiffening agent or the solidifying agent that is used for Resins, epoxy.The amine that many commercializations are arranged at present can make the resin of high Tg as stiffening agent or solidifying agent, but they all are alicyclic or aromatic diamine usually.Amine and available from Dow Chemical (Dow Chemical Company, some examples of the Tg of the resin that makes when Midland, MI) D.E.R.331 epoxy resin cure comprise hexanaphthene-1,2-diamines (Tg:152 ℃); Isophorone diamine (IPDA) (147 ℃); And 4-((4-aminocyclohexyl) methyl) hexahydroaniline (163 ℃).The aliphatic diamine of straight chain can be used as stiffening agent, but can't make the resin with high Tg usually.The example of aliphatic diamine has Dytek (Tg:104 ℃), AEP (Tg:106 ℃) and TMD (Tg:104 ℃).Similarly, because the temperature that amino alcohol can be cured is lower than the temperature that simple amine can be cured, and these amine also can't form the solidified Resins, epoxy with high glass-transition temperature (Tg), so at present with stiffening agent or the solidifying agent of amino alcohol as commercialization.The modal example of some of amino alcohol includes, but are not limited to thanomin (EA), diethanolamine (DEA), (it can be available from ANGUS Chemical of Buffalo Grove for 2-amino-2-methyl-1-propanol (AMP), Illinois, USA) and 2-amino-2-ethyl-1, ammediol (AEPD) [Asghar checks the Tg data that whether have any of these amino alcohol] (also can be available from ANGUS Chemical of Buffalo Grove, Illinois, USA) etc.Well-known and the frequent amine hardener system of using includes, but are not limited to isophorone diamine (IPDA), m-xylenedimaine (MXDA), aminoethylpiperazine (AEP), quadrol etc. in the industry.Therefore, reported use TRIS-AMINO in patent documentation, it is the non-volatile alkanolamine with primary amine functional group, can be available from ANGUS Chemical of Buffalo Grove, Illinois, USA.No. the 4330644th, 3607833 and 7001938, United States Patent (USP), and U.S. Patent Application Publication has all been described the application of TRIS-AMINO in various epoxy-based compositions for US2007/0065669 number.
But the many amino alcohol radical stiffening agent that uses can only provide second-order transition temperature less than about 120 ℃ solidified Resins, epoxy at present, therefore, often is not suitable for high temperature and uses.The amino alcohol radical stiffening agent that can make the resin with the high glass-transition temperature (promptly greater than about 120 ℃) that is applicable to that high temperature is used will be very valuable.With respect to simple aliphatic amine, the attendant advantages of amino alcohol is, owing to have alcohol functional group, the character that is improved.Predict according to document, because hydroxyl and the interaction that applies the surface of coating, epoxy coat has bond properties.And also known hydroxyl has catalytic effect in cure profile, can solidify (referring to No. the 3943104th, United States Patent (USP) for example) thus at lesser temps.
Summary of the invention
The invention provides a kind of solidified resin system, it comprises: (a) at least a Resins, epoxy of 35-90 weight %; (b) the diamino alcohol compound of 0.1-35% with following formula:
Figure BSA00000410078700031
Wherein, R is hydrogen, alkyl or aryl independently; R 1Be hydrogen or alkyl independently; Perhaps R and R 1Can be joined together to form cycloalkyl; R 2Be hydrogen, alkyl or aryl independently; R 3Be hydrogen, alkyl or aryl independently; R 4Be hydrogen or alkyl independently; Perhaps R 3And R 4Can be joined together to form cycloalkyl; Wherein all wt percentage ratio is benchmark in the gross weight of solidified resin system all.Described Resins, epoxy can be one or more compounds that are selected from down group: cycloaliphatic epoxides, cycloaliphatic epoxides with glycol modification, epoxy-Novolak resin (epoxy phenolic novolac resin), multifunctional (poly-epoxy) Resins, epoxy, dihydroxyphenyl propane basic ring epoxy resins and Bisphenol F basic ring epoxy resins.
In a kind of embodiment of solidified resin system of the present invention, Resins, epoxy comprises the mixture of at least two kinds of Resins, epoxy.
In a kind of concrete embodiment, the diamino alcohol compound can be 2-nitropropane and the product that is selected from a kind of aldehyde of crotonic aldehyde and phenylacrolein.For example, R, R 1, R 2, R 3And R 4Each is methyl naturally.
The present invention also provides a kind of method for preparing curable resin system, and it comprises the following component of mixing: (a) at least a Resins, epoxy of 35-65 weight %; (b) the diamino alcohol compound of 0.1-35 weight % with following formula:
Figure BSA00000410078700032
Wherein R is hydrogen, alkyl or aryl independently; R 1Be hydrogen or alkyl independently; Perhaps R and R 1Can be joined together to form cycloalkyl; R 2Be hydrogen, alkyl or aryl independently; R 3Be hydrogen, alkyl or aryl independently; R 4Be hydrogen or alkyl independently; Perhaps R 3And R 4Can be joined together to form cycloalkyl; Wherein all wt percentage ratio is all based on the gross weight of solidified resin system.Described Resins, epoxy can be one or more compounds that are selected from down group: cycloaliphatic epoxides, with the cycloaliphatic epoxides of glycol modification, epoxy-Novolak resin, multifunctional (poly-epoxy) Resins, epoxy, dihydroxyphenyl propane basic ring epoxy resins and Bisphenol F basic ring epoxy resins.
In a kind of embodiment of method of the present invention, Resins, epoxy comprises the mixture of at least two kinds of Resins, epoxy.
In a kind of concrete embodiment of the inventive method, the diamino alcohol compound can be 2-nitropropane and the product that is selected from a kind of aldehyde of crotonic aldehyde and phenylacrolein.For example, R, R 1, R 2, R 3And R 4Each is methyl naturally.
Detailed Description Of The Invention
The invention provides the new useful aminocompound of a class, i.e. diamino alcohol, with and manufacture method.These compounds are by series connection Michael reaction and nitro alkane and one or more α, and the Henle reaction of beta-unsaturated aldehyde is also optional to be made with the aldehyde reaction of formaldehyde and so on subsequently.Described compound is represented with following formula:
Figure BSA00000410078700041
Wherein R be independently hydrogen, alkyl, aryl or-CH 2OH; R 1Be independently hydrogen, alkyl or-CH 2OH; Perhaps R and R 1Can be joined together to form cycloalkyl; R 2Be the phenyl of hydrogen, methyl, alkyl, phenyl or replacement independently; R 3Be independently hydrogen, alkyl, phenyl or replacement phenyl or-CH 2OH; R 4Be independently hydrogen, alkyl or-CH 2OH; Perhaps R 3And R 4Can be joined together to form cycloalkyl.
The diamino alcohol of above classification comprises the polyvalent alcohol and the simple diamino monohydroxy-alcohol of various degree.Better simply diamino monohydroxy-alcohol has following formula:
Wherein R is the phenyl of hydrogen, alkyl, phenyl or replacement independently; R 1Be hydrogen or alkyl independently; Perhaps R and R 1Can be joined together to form cycloalkyl; R 2Be the phenyl of hydrogen, alkyl or phenyl or replacement independently; R 3Be hydrogen, alkyl or aryl independently; R 4Be hydrogen or alkyl independently; Perhaps R 3And R 4Can be joined together to form cycloalkyl.
Diamino monohydroxy-alcohol of the present invention can pass through nitro alkane and α, and the reaction of beta-unsaturated aldehyde makes, and this reaction generates intermediate dinitrobenzene alkylol cpd.This reaction is under atmospheric pressure carried out under 0-100 ℃ temperature usually, for example but be not limited to 0-50 ℃.The applicant finds in surprise and expediently, at first carry out the Michael reaction of nitro alkane, carry out described this reaction subsequently, carry out aldol condensation (Henry) reaction then, wherein the second nitro alkane is added in the aldehyde, make single dinitrobenzene monohydroxy-alcohol intermediate.
The nitro alkane can be uncle's nitro or the secondary nitro alkane with following formula:
Figure BSA00000410078700051
Wherein R is a hydrogen, R 1It is the phenyl of hydrogen, alkyl, phenyl or replacement; Perhaps wherein R is the phenyl of alkyl, phenyl or replacement, R 1It is alkyl; Perhaps R and R 1Can be joined together to form cycloalkyl.For example but to be not limited to Nitromethane 99Min., nitroethane, 2-nitropropane, nitrocyclohexane etc. all be to be suitable as parent material to prepare nitro alkane according to diamino alcohol compound of the present invention.More particularly, uncle's nitro or secondary nitro alkane can be C 1-C 20Nitro alkane, C 1-C 10Nitro alkane or C 2-C 6The nitro alkane.
Suitable α, beta-unsaturated aldehyde has following formula:
Figure BSA00000410078700052
Wherein R is the phenyl of hydrogen, methyl (alkyl), phenyl or replacement.Suitable unsaturated aldehyde includes, but are not limited to propenal, crotonic aldehyde, phenylacrolein, the cinnamylaldehyde derivatives that replaces at aromatic ring etc.
Aforementioned nitro alkane that carries out in succession and the Michael-Henle reaction between the unsaturated aldehyde take place in the presence of suitable catalyst, described catalyzer comprises but is not limited to organic bases, for example 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene (" DBU "), 2-dimethylamino-2-methyl isophthalic acid-propyl alcohol (" DMAMP "), Trimethylamine (TMA), dimethyl isopropylamine (DMIPA), N, N, N ', N '-tetramethyl guanidine (TMG), Verkade alkali etc.Perhaps, can also use mineral alkali such as salt of wormwood and sodium hydroxide catalyzer as above-mentioned Michael-Henle reaction in succession.
In the parent material that provides, the mol ratio of nitro alkane and aldehyde is generally 2: 1.According to implementer's hobby, can carry out this reaction under the situation of solvent having solvent or do not have.Suitable solvent includes, but are not limited to tetrahydrofuran (THF), 2-methyltetrahydrofuran, two
Figure BSA00000410078700053
Alkane.
When required product is the diamino polyol compound, (1) the nitro alkane is uncle's nitro alkane, the process of making the diamino polyol compound further is included in (1) uncle nitro alkane and (2) α, after the beta-unsaturated aldehyde reaction, still before the nitroalcohol that reduction makes, make the nitroalcohol that makes further with (3) aldehyde reaction, described (3) aldehyde for example is formaldehyde, to form the dinitrobenzene polyol compound, then in the presence of hydrogenation conditions and catalyzer with its further reduction.
More particularly, make following the carrying out of process of diamino polyol compound: (A) make (1) uncle nitro alkane and (2) α, the beta-unsaturated aldehyde reaction forms dinitrobenzene alcohol; (B) further make dinitrobenzene alcohol and (3) aldehyde (for example formaldehyde) reaction form dinitrobenzene polyvalent alcohol (for example dinitrobenzene glycol or dinitrobenzene triol) product; (C) then in the presence of hydrogenation conditions and catalyzer further reduction dinitrobenzene polyvalent alcohol product form corresponding diamino polyvalent alcohol product.This reaction is carried out under certain condition, make that (that is, temperature is 0-100 ℃, under atmospheric pressure greater than the speed of Henle reaction for the speed of Michael reaction of nitro alkane, for example but be not limited to 0-50 ℃), thereby react in succession to generate the dinitrobenzene polyvalent alcohol.(1) nitro alkane that provides in first reactions steps that generates dinitrobenzene alcohol and the mol ratio of (2) aldehyde are 2: 1.Uncle's nitro alkane can be uncle C 1-C 20The nitro alkane, for example but be not limited to uncle C 1-C 10The nitro alkane.α, beta-unsaturated aldehyde can be selected from down group: propenal, crotonic aldehyde, phenylacrolein and the cinnamylaldehyde derivatives that replaces at aromatic ring.
Dinitrobenzene alcohol confirms that with being reflected at of second aldehyde (as formaldehyde) reaction of formation nitroalcohol after finishing (for example confirming that by the known analytical procedure of those of ordinary skills described method includes, but are not limited to gas-chromatography or high performance liquid chromatography) takes place subsequently.For this reactions steps subsequently, the ratio of formaldehyde and dinitrobenzene alcohol is generally 2: 1.Equally, this reaction can be carried out under the situation of solvent having solvent or do not have according to implementer's hobby, and described solvent for example is but is not limited to tetrahydrofuran (THF), 2-methyltetrahydrofuran, dioxane.
The intermediate dinitrobenzene alkylol cpd that generates by above-mentioned any Michael-Henle reaction in succession has following formula:
Figure BSA00000410078700061
Wherein R be independently hydrogen, alkyl, aryl or-CH 2OH; R 1Be independently hydrogen, alkyl or-CH 2OH; Perhaps R and R 1Can be joined together to form cycloalkyl; R 2Be hydrogen, methyl, alkyl, phenyl or substituted-phenyl independently; R 3Be independently hydrogen, alkyl, phenyl or substituted-phenyl or-CH 2OH; R 4Be independently hydrogen, alkyl or-CH 2OH; Perhaps R 3And R 4Can be joined together to form cycloalkyl.
In a kind of concrete embodiment, the nitro alkane is the 2-nitropropane, and α, beta-unsaturated aldehyde are crotonic aldehyde or phenylacrolein, generates dinitrobenzene monohydroxy-alcohol compound.
Dinitrobenzene alcohol intermediate (monohydroxy-alcohol or polyvalent alcohol) further reduction in the presence of hydrogenation conditions and suitable catalyst then generates the required diamino alcohol that comprises two amino, and each amino all links to each other with tertiary carbon atom.Suitable dehydrogenation catalyst includes, but are not limited to Raney nickel, perhaps platinum base or palladium-based catalyst (for example the platinum of element form or oxide form or palladium have carrier such as carbon or do not have carrier).Other appropriate reductant include, but are not limited to metal/acid combination, for example iron/acetate; And aluminum hydride.An example that is fit to dehydrogenation catalyst system used according to the invention is combination arbitrarily in hydrogen and Raney nickel, platinum or the palladium.
The hydrogenation of dinitrobenzene alcohol can be carried out under 30-100 ℃ temperature under the pressure of 100-1000 pound/square inch (" psi ") with the process that generates diamino alcohol.Can use solvent, described solvent for example is but is not limited to tetrahydrofuran (THF) or methyl alcohol.
Diamino alcohol of the present invention is the suitable stiffening agent of epoxy-resin systems, and wherein some can make second-order transition temperature (Tg) greater than 120 ℃ solidified Resins, epoxy.These curable epoxy-resin systems can form by mixing following component: at least a Resins, epoxy, diamino alcohol mentioned above, and optional catalyzer, other stiffening agents, toughner, fire retardant and those of ordinary skills are known and other additives of using.Temperature that then can be by being exposed to rising, exposing to the sun to penetrating in UV-light etc. is cured curable epoxy-resin systems, for example but be not limited to and depend on that the concrete kind of used Resins, epoxy and expection thereof use.
Can any appropriate method known by those of ordinary skills and that implement measure glass transition temperature Tg, described method includes, but are not limited to dsc (DSC) or dynamic mechanical analysis (DMTA), as described in ASTM D5045.
Can for example use the NewCastle from T.A.Instruments of by the dsc measurement second-order transition temperature, the Q100 dsc measurement equipment that Delaware, USA buy carries out, and this equipment prepares to carry out 10 ℃/minute scanning.Sample size remains on below 15 milligrams usually.Perforated sealing pad holds sample in the use lid in the DSC pond.The DSC scanning result is analyzed, adopted the tangential method of half extrapolation to determine final Tg (Tg analysis).
Measuring second-order transition temperature by DMTA can for example carry out according to ASTM D5045, and radian frequency is 1 hertz (Hz), and 0.1% strain is carried out on three rectangle samples.For the temperature range that these embodiment select can be at 30-2800 ℃.It is long that sample size is generally 17 millimeters (mm), 13 mm wides and 4 mm thick.Sample is inserted between adjustable anchor clamps, use the closed anchor clamps of dial torque wrench.With torsional mode sample is vibrated then.Sample applied 3 ℃/minute dynamic intensification.Can adopt slower heating rate with maintenance thermal equilibrium, and consider the thermal mass of sample.Record storage modulus and out-of-phase modulus and tangent Δ.
Solidified resin system according to the present invention comprises: (a) at least a Resins, epoxy of 35-90 weight %; (b) the diamino alcohol compound of 0.1-35 weight % with following formula:
Figure BSA00000410078700081
Wherein R is hydrogen, alkyl or aryl independently; R 1Be hydrogen or alkyl independently; Perhaps R and R 1Can be joined together to form cycloalkyl; R 2Be hydrogen, alkyl or aryl independently; R 3Be hydrogen, alkyl or aryl independently; R 4Be hydrogen or alkyl independently; Perhaps R 3And R 4Can be joined together to form cycloalkyl; Wherein all wt percentage ratio is benchmark in the gross weight of solidified resin system all.
As those of ordinary skills know with limit of power in, think that with respect to Resins, epoxy be according to " significant quantity " of the present invention to the amounts of stoichiometric diamino alcohol stiffening agent at most.More particularly, calculating the stoichiometry of diamino alcohol stiffening agent in the following manner, will be that the equivalents of benchmark is added together in the weight with respect to interchangeable in the used amino alcohol-NH base.In general, also as one of ordinary skill in the understanding, the amount of the diamino alcohol stiffening agent of required higher molecular weight is less than the amount of the diamino alcohol stiffening agent of lower molecular weight.For example, generate according to epoxy-resin systems of the present invention, be 35 weight % for the appropriate amount by crotonic aldehyde deutero-diamino alcohol stiffening agent, replaces if use by phenylacrolein deutero-diamino alcohol stiffening agent, and then its appropriate vol is less than 35 weight %.
Preferred diamino alcohol as the stiffening agent in the epoxy-resin systems is the diamino alcohol that those amine functional groups wherein link to each other with tertiary carbon, for example has the compound of following formula:
These materials obtain by two steps as described in detail above in the following manner, make 1 mole of phenylacrolein or crotonic aldehyde and 2 moles of 2-nitropropane reactions, use Raney nickel catalyst to carry out hydrogenation then.
The most effective diamino alcohol that epoxy-resin systems with high Tg is provided is R wherein 2Be alkyl chain or phenyl and R, R 1, R 3With R 4It is the diamino alcohol of methyl.
Can use multifunctional diamino alcohol as the stiffening agent system,, finally make high Tg material (Tg is greater than 140 ℃) to solidify multiple Resins, epoxy.Adding has some described diamino alcohols especially the Tg that reported of the solidified epoxy-resin systems of 2-nitropropane adducts is greater than the Tg of the epoxy material that contains conventional amino alcohol stiffening agent, and the former Tg is higher 20 ℃ than the latter's Tg at least.This is particularly advantageous in high temperature is used.In addition, these materials can be cured very efficiently, do not have highdensity hydroxyl, and the water that is therefore attracted is less, thereby provide better overall character for final system.
Two amine functional groups provide a plurality of sites for cured epoxy resin, therefore allow a plurality of epoxy group(ing) to utilize 1 mole of diamino alcohol to react, thereby produce several new secondary alcohol (secondary alchol) site in epoxy systems.This situation is favourable, because people's there's a widespread conviction that secondary alcohol helps lend some impetus in the epoxy coated preparation metal is bonding.Do not wish to be subject to theory, believe that also alcohol functional group has catalytic effect in solidification process.Similarly, Resins, epoxy is controlled with respect to the stoichiometry of diamines, make the solidified resin keep the secondary amine functional groups of high density, estimate that this way also can improve the binding property of this resin to the surface, thereby in bonding and these two kinds of very important application of character of Tg, make strong adherent high Tg resin.
Equally, do not wish to be subject to theory, notable feature of the present invention is that diamino alcohol of the present invention has a plurality of amidos but not a plurality of hydroxyl, more is usually used in situation in the epoxy systems as aminocompound.Effective curing of resin can be provided like this, also allow the length by changing alkyl chain that the main chain of two amine hardeners is improved.This technology also allows to add any required functional group, for example amine of phenyl, alkyl, hydroxyl and any degree (primary amine, secondary amine or tertiary amine) under the condition of Tg helping controlling.
And the above-mentioned synthetic method that is used for preparing diamino alcohol allows required functional group is arranged on molecule carefully.This synthetic method can be formed in suitable compactness but the diamines that has high amine functionality in the molecule that highly replaces.Can be used to make up the character of the nitro paraffin alkane of molecule by change, change the Tg value of solidified Resins, epoxy.
Diamino alcohol can be used for the Resins, epoxy of any kind of, this means, this term comprises one or more reactive ethylene oxide group (C as used in this article 2H 3O) compound is referred to herein as " epoxy group(ing) " or " epoxy-functional ".Suitable Resins, epoxy comprises that those comprise the compound of at least one adjacent epoxy group(ing).Resins, epoxy can be saturated or undersaturated, alicyclic, aromatics or heterocycle family, can replace.Resins, epoxy can also be monomer or polymeric.
More particularly, be applicable to that Resins, epoxy of the present invention for example comprises but is not limited to cycloaliphatic epoxides, cycloaliphatic epoxides with glycol modification, epoxy-Novolak resin, multifunctional (poly-epoxy) Resins, epoxy, dihydroxyphenyl propane basic ring epoxy resins and Bisphenol F basic ring epoxy resins, and their mixture etc.
Cycloaliphatic epoxides comprises for example diepoxide of the alicyclic ester of dicarboxylic acid, for example oxalic acid two (3,4-epoxycyclohexyl methyl) ester, hexanodioic acid two (3,4-epoxycyclohexyl methyl) ester, vinyl cyclohexene diepoxide and Dicyclopentadiene (DCPD) diepoxide.Commercially available cycloaliphatic epoxy resin comprises that commodity are called 3 of ERL, D.E.R. and D.E.N., 4-epoxycyclohexyl methyl-3,4-epoxycyclohexane carboxylate and other cycloaliphatic epoxy resins, these products all can be from (the Dow Chemical Company of Midland of Dow Chemical, Michigan USA) buys.In addition, CELLOXIDE 2021, CELLOXIDE 2021P, EPOLEAD GT301 are can be from Daicel Chemical Industries, the cycloaliphatic epoxy resin that Ltd of Japan is purchased.Cycloaliphatic epoxides with glycol modification comprises the aliphatic epoxy material of for example using polypropylene glycol modified, epoxidised polyhutadiene comprises the silicone resin of epoxy-functional, epoxy vinyl ester resin, (glycidated) resin of Racemic glycidolization, epoxidised wet goods.ERL-4299 (two (3, the 4-epoxycyclohexyl) adipic acid ester) can buy from Dow Chemical (Dow Chemical Company), CELLOXIDE 2080 series ((3 ', 4 '-epoxy cyclohexane) methyl 3 ', the caprolactone of 4 '-epoxycyclohexyl-carboxylicesters modification) can be from Daicel Chemical Industries, Ltd. buys.
Be applicable to that epoxy-Novolak resin of the present invention includes, but are not limited to phenol and the condenses of formaldehyde, for example phenolic varnish, dihydroxyphenyl propane varnish and the cresols varnish that obtains under acidic conditions.Polyfunctional epoxy resin for example comprises but is not limited to Resorcinol diglycidyl ether (1,3-two-(2, the 3-glycidoxy) benzene), triglycidyl group is right-and amino phenol (4-(2, the 3-glycidoxy)-N, N-two (2, the 3-epoxypropyl) aniline), based on the polyepoxides of aromatic amine and Epicholorohydrin N for example, N '-diglycidyl-aniline, N-diglycidyl-4-aminophenyl etc., and the mixture of these compounds.
Be applicable to that other Resins, epoxy of the present invention include, but are not limited to 4,4 '-dihydroxyl phenylbenzene dimethylmethane (being dihydroxyphenyl propane), two (4-hydroxyl phenol) methane (being Bisphenol F), the diglycidyl ether of Bisphenol F, and based on other resins of dihydroxyphenyl propane and Bisphenol F.D.E.R.332, D.E.R.383 and D.E.R.331 are the dihydroxyphenyl propane basic ring epoxy resins of buying from Dow Chemical (Dow Chemical Company).D.E.R.354 and D.E.R.354LV also are the Bisphenol F basic ring epoxy resins of buying from Dow Chemical (Dow Chemical Company).
These materials can be used for other stiffening agents and/or catalyst system according to application.This material also can be by at first with LER (liquid epoxies) reaction, use reaction product in the final epoxy resin formulation then, thereby as " stiffening agent of modification " or prepolymer.
According to also comprising other stiffening agents or solidifying agent in the resin system of the present invention.Suitable amine and/or amide hardener comprise that those comprise the compound of primary amine part, and the compound that comprises two or more primary amine that link to each other with the central organic moiety of common or secondary amine or primary amide or secondary amide part.The suitable example that contains amine hardener comprises amino alcohol, quadrol, diethylenetriamine, polypropyleneoxide diamine, Triethylenetetramine (TETA), Dyhard RU 100 (dicyandiamide), trimeric cyanamide, hexahydroaniline, benzylamine, Diethyl Aniline, methylene dianiline (MDA), between-phenylenediamine, diamino diphenyl sulfone, 2,4 two (right-aminobenzyl) aniline, piperidines, N, N-diethyl-1,3-propylene diamine etc., and the solubility adducts and the salt thereof of amine and polyepoxide.The suitable amide solidifying agent comprises Dyhard RU 100 and poly-amino amine (polyamidoamine).Poly-amino amine is the reaction product of polyacid and amine normally.
In addition, the present invention can use thiol-cured dose.As used herein, " mercaptan " also comprises polythiol (polythiol, polymercaptan) solidifying agent.Suitable mercaptan includes, but are not limited to aliphatic mercaptan such as first two mercaptan, dimercaptopropane, hexanaphthene two mercaptan, 2-mercaptoethyl-2,3-dimercaptosuccinic acid(DMSA) ester, glycol ether two (2-mercaptoacetate), tetramethylolmethane three (thioglycolic acid ester), aromatic mercaptans is as two, three or four sulfydryl benzene, dimercapto biphenol, toluene two mercaptan etc.
Can in composition epoxy resin, add other accelerators or catalyzer.Accelerator comprises those compounds of the reaction of catalysis Resins, epoxy and solidifying agent.Accelerator be comprise amine, phosphine, heterocyclic nitrogen, ammonium,
Figure BSA00000410078700111
(phosphonium), Arsenic (arsonium) or sulfonium (sulfonium) part compound.Its example comprises imidazoles, imidazolidine and tetrahydroglyoxaline.Other catalyzer comprise radical initiator, and for example azo-compound comprises azo isobutyronitrile, and organo-peroxide, for example t-butylperoxyl benzoate, the sad tert-butyl ester of mistake, methylethyl ketone peroxide, acetyl peroxide acetate and benzoyl peroxide etc.
Also can comprise flame-retardant additive according to resin system of the present invention, include, but are not limited to additive such as the tetrabromo-bisphenol (TBBA) and the derivative thereof of bromination, with the additive of non-bromination as by DOP (9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene 10-oxide compound) and the derived compounds for example condensation product, the derivative of phenolic varnish of DOP-quinhydrones, DOP and glycidyl ether, and inorganic combustion inhibitor for example aluminum trihydrate and phospho acid aluminium.
Also can comprise toughner according to resin system of the present invention, be used to reduce the fragility of solidified resin system.Toughner includes, but are not limited to the rubber compounding thing, segmented copolymer (as amphiphilic block copolymer), the divinyl of carboxy blocking, polysulfide base toughner, end capped butadiene-nitrile of amine and polythioether.As well known to persons of ordinary skill in the art with understand, the content of toughner is that benchmark is counted 0.1-30 weight % with the gross weight of resin system in the epoxy-resin systems.
Also can comprise conventional known additives and filler in the resin system of the present invention.These additives and filler can comprise for example boric acid, silicon oxide, glass, talcum, metal-powder, wetting agent, pigment, tinting material, releasing agent, coupling agent, ion scavenger, UV stabilizer, toughner and tackifier.These components also can comprise other resins such as polyol resin, vibrin, resol, and other reagent for example are used to reduce viscosity and promotion is stable, and these all are well-known in the industry.
Embodiment
Embodiment 1
Synthetic 2,5,6-trimethylammonium-2,6-dinitrobenzene heptan-3-alcohol (dinitrobenzene alcohol intermediate)
Figure BSA00000410078700121
To being equipped with stirring rod, thermopair, being stamped the DBU that adds 2-nitropropane (" 2-NP ") (50 grams, 0.56 mole, 5.0 equivalents) and catalytic amount in the three neck round-bottomed flasks of the feed hopper of nitrogen inlet and condenser.Under nitrogen atmosphere, yellow solution was mixed about 30 minutes.In this mixture, dropwise added crotonic aldehyde (7.9 grams, 9.2 milliliters, 0.112 mole, 1.0 equivalents) in the clock time at 20 minutes.Add crotonic aldehyde under following three kinds of different conditions, all these situations all obtain identical result.
Condition:
A: when the 2-NP/DBU mixture is in-30 ℃, dropwise add crotonic aldehyde, and be warming up to room temperature.
B: when the 2-NP/DBU mixture is in 20 ℃, dropwise add crotonic aldehyde, and be warming up to room temperature.
C: when the 2-NP/DBU mixture is in room temperature, dropwise add crotonic aldehyde.
In each situation, after reinforced the finishing, at room temperature with reactant stir about 5-6 hour.During this period of time, the adularescent solid precipitation leaves solution.At this moment, GC analyzes in the demonstration reaction mixture and exists without any crotonic aldehyde.Under room temperature and nitrogen atmosphere the reaction mixture stirring is spent the night, by the isolated by vacuum filtration white solid, water thoroughly washs this solid.With the solid air drying, then 45 ℃ of vacuum-dryings.The overall yield of required nitroalcohol is 72% (27.8 gram).Nucleus magnetic resonance test (" NMR ") and liquid chromatography (LC) show that product purity is greater than 99%. 1H?NMR(CDCl 3)：δ0.82-1.56(m，18H)，4.02-4.07(m，1H)。 13C NMR (CDCl 3): δ 14.1,20.7, and 22.5,23.1,23.6,33.5,37.9,73.1,91.8 and 92.1ppm.Also carry out this reaction in the less condition of the mol ratio of unsaturated aldehyde and nitro alkane.When unsaturated aldehyde is 1: 2.9 with respect to the ratio of nitro alkane, obtain similar result with above embodiment.
Synthetic 2,6-diamino-2,5,6-trimethylammonium heptan-3-alcohol (diamino alcohol)
Figure BSA00000410078700122
The above-mentioned nitroalcohol of 25 grams is dissolved in 200 ml methanol, in autoclave,, uses 14.2 gram RaNi 3111, under 600psi pressure, carry out hydrogenation as catalyzer at 60 ℃.After comprising filtering catalyst and removing the aftertreatment of methyl alcohol, obtain about 11 gram (59% productive rate) low viscosity light green/colourless liquids.There is required amino alcohol in NMR and gas chromatography-mass spectrum (" GC-MS ") analysis confirmation.Chemical ionization mass spectrometry CI-MS shows [M+H]=189, and GC shows that this material purity is 94%.Under 0.5-1.5 holder condition, the boiling point of this material is about 110-120 ℃. 1H?NMR(CDCl 3)：δ0.48-1.22(m，18H)，2.84-2.89(m，1H)。 13C NMR (CDCl 3): δ 16.8,25.2, and 27.9,30.8,34.7,42.2,51.8,52.8 and 77.3ppm.The diamino alcohol product of this embodiment 1 is labeled as " CROT-AMP-NH2 " in following table.
Embodiment 2
Synthetic 6-methyl-3,7-dinitrobenzene ninth of the ten Heavenly Stems-4-alcohol (dinitrobenzene alcohol intermediate)
Figure BSA00000410078700131
To being equipped with stirring rod, thermopair, being stamped the DBU that adds 2-nitropropane (50 grams, 0.56 mole, 5.0 equivalents) and catalytic amount in the three neck round-bottomed flasks of the feed hopper of nitrogen inlet and condenser.Under nitrogen atmosphere, deep yellow solution was mixed about 30 minutes.In this mixture, dropwise added crotonic aldehyde (7.9 grams, 9.2 milliliters, 0.112 mole, 1.0 equivalents) in the clock time at 20 minutes.In this case, carry out the reinforced of crotonic aldehyde in room temperature, in reinforced process, the heat release of observing about 12-15 ℃ heats up.After reinforced the finishing, reacted 6 hours in room temperature with under stirring.At this moment GC analyzes in the demonstration mixture and does not have crotonic aldehyde.At room temperature reactant is stirred and spend the night, high performance liquid chromatography (HPLC) is analyzed demonstration and is only had two peaks, and they are corresponding to excessive 1-NP and required product (1CA+2NP adducts).Remove excessive 1-NP by vacuum distilling, the tangerine look viscous liquid that obtains is carried out hydrogenation.The gross weight of this material is about 37.2 grams, still remaining 1-NP.
Synthetic 3,7-diamino-6-methyl ninth of the ten Heavenly Stems-4-alcohol (diamino alcohol intermediate)
Figure BSA00000410078700132
The above-mentioned nitroalcohol of 37.2 grams is dissolved in 50 ml methanol, in autoclave, under hydrogen atmosphere,, uses 14.3 gram RaNi 3111, under 600psi pressure, carry out hydrogenation as catalyzer in 60 ℃.After comprising filtering catalyst and removing the processing of methyl alcohol, obtain about 18 gram (64% productive rate) low viscosity yellow liquids.There is required amino alcohol in the GC-MS analysis confirmation.CI-MS shows [M+H]=189, and GC shows that the purity of this material is 50%.Remaining is the lower boiling material.
Embodiment 3
Synthetic 2,6-dimethyl-2,6-dinitrobenzene-5-phenyl heptan-3-alcohol (dinitrobenzene alcohol intermediate)
To being equipped with stirring rod, thermopair, being stamped the DBU that adds 2-nitropropane (101.1 grams, 1.14 moles, 6.0 equivalents) and catalytic amount in the three neck round-bottomed flasks of the feed hopper of nitrogen inlet and condenser.Under nitrogen atmosphere, yellow solution was mixed about 20 minutes.In this mixture, dropwise added anti-phenylacrolein (25.0 grams, 0.19 mole, 1.0 equivalents) in the clock time at 20 minutes.In nitro paraffin alkane, adding in the process of anti-phenylacrolein, observe about 22 ℃ heat release.After reinforced the finishing, reaction mixture is heated to 50 ℃ and kept 4 hours.After this heat-up time, make the slow cool to room temperature of mixture.When reaction mixture temperature reaches 36.8 ℃, there is the light yellow solid precipitation to leave solution.Cross filter solid with B, thoroughly wash with pentane and ether.Make white powder under vacuum condition dry 1 hour.The overall yield of required nitroalcohol is 62% (36 gram).NMR shows that product purity is greater than 99%. 1H?NMR(CDCl 3)：δ1.45-2.27(m，15H)，3.52-3.54(m，1H)，3.67-3.74(m，1H)，7.17-7.34(m，5H)。 13C?NMR(CDCl 3)：δ20.8，22.4，23.2，25.8，31.3，50.3，72.9，91.5，91.6，128.1，128.7，129.4，136.6ppm。
Synthetic 2,6-diamino-2,6-dimethyl-5-phenyl heptan-3-alcohol (diamino alcohol)
Figure BSA00000410078700142
The above-mentioned nitroalcohol of 50 grams is dissolved in 300 ml methanol, in autoclave,, uses 24.3 gram RaNi 3111, under 600psi pressure, carry out hydrogenation as catalyzer at 60 ℃.Comprise filtering catalyst and remove the aftertreatment of methyl alcohol after, obtain about 40 the gram (68% productive rate) high viscosity light yellow/colourless liquid.There are required amino alcohol in NMR and GC-MS analysis confirmation.CI-MS shows [M+H]=251, and GC shows that this material purity that directly obtains from autoclave is 78%.The remainder of this material looks it is the single adducts (mono adduct) that is obtained by the reversible reaction of Henle reaction).By this mixture of vacuum distilling purifying, the purity that obtains material requested is about 96.2%.Under 0.9-1.1 holder condition, the boiling point of this material is about 145-155 ℃. 1H?NMR(CDCl 3)：δ0.91-0.99(m，12H)，1.67-1.81(m，3H)，2.71-2.76(m，2H)，7.08-7.23(m，5H)。 13C?NMR(CDCl 3)：δ24.6，27.9，28.3，29.8，31.6，51.8，52.6，54.2，75.9，126.3，127.8，129.4，142.0ppm。
The diamino alcohol product of this embodiment 3 is labeled as " CINNAM-AMP-NH2 " in following table.
Embodiment 4
Epoxy preparation
Following table is the summary of cure profile and second-order transition temperature data.The material that has amine on tertiary carbon has high Tg value.Material with aromatic ring has the highest Tg in institute's screening material.This work uses non-isothermal dsc (DSC) to carry out.
DSC by research to the hot-fluid of sample along with variation of temperature, be widely used in the cure kinetics of these epoxy systems of research, wherein use the D.E.R. of Tao Shi TM331 as matrix resin.This is a kind of general applications resin that is widely used in the industry, is considered to carry out the good starting point of preliminary study.Obtain the DSC Thermogram of resin and stiffening agent mixture.Can utilize the indication of heat release behavior as the observing response process.Carried out after the curing reaction, can carry out another DSC test, to obtain Tg at once with this part cooling.Use TA instrument Q100 type differential scanning calorimeter to carry out dsc analysis.Instrument is linked to each other with automatic sampler with the refrigerated cooling system.The premixed even viscous mixt of 10-20 milligram is placed large volume (100 microlitre) stainless steel tray, close with cap seal.At ambient temperature the sample tray is placed the DSC sample pool, also the tray with a sky places the DSC reference cell.From room temperature to 250 ℃ scope under the nitrogen purging condition heating rate with 10 ℃/minute heat.Use the solidifying agent of stoichiometry, and calculate by the quantity of active amine hydrogens.Some commercial stiffening agents that use with D.E.R.331 (comparative example) provide following Tg value:
D.E.R.24 (Tg:129.5 ℃); Trimethylammonium hexanediamine-TMD (Tg:104 ℃); Aminoethylpiperazine-AEP (Tg:106 ℃); IPD (Tg:147 ℃); Hexanaphthene two (methylamine) (Tg:130 ℃); Dytek A (Tg:104 ℃); Encamine MCA (Tg:62 ℃);
Table
Figure BSA00000410078700161

Claims (12)

1. solidified resin system, it comprises:
(a) at least a Resins, epoxy of 35-90 weight %; With
(b) the diamino alcohol compound of 0.1-35 weight % with following formula:
Figure FSA00000410078600011
Wherein R is hydrogen, alkyl or aryl independently; R 1Be hydrogen or alkyl independently; Perhaps R and R 1Can be joined together to form cycloalkyl; R 2Be hydrogen, alkyl or aryl independently; R 3Be hydrogen, alkyl or aryl independently; R 4Be hydrogen or alkyl independently; Perhaps R 3And R 4Can be joined together to form cycloalkyl; Wherein all wt percentage ratio is benchmark in the gross weight of solidified resin system all.
2. solidified resin system as claimed in claim 1 is characterized in that described at least a Resins, epoxy comprises the mixture of at least two kinds of Resins, epoxy.
3. solidified resin system as claimed in claim 1 is characterized in that the second-order transition temperature of described solidified resin system is greater than 120 ℃.
4. solidified resin system as claimed in claim 1 is characterized in that, described diamino alcohol compound is 2-nitropropane and the reduzate that is selected from a kind of aldehyde in crotonic aldehyde and the phenylacrolein.
5. solidified resin system as claimed in claim 1 is characterized in that, wherein R, R 1, R 3And R 4Each is alkyl naturally, R 2Be methyl or phenyl, the second-order transition temperature of described solidified resin system is greater than 120 ℃.
6. solidified resin system as claimed in claim 1, it is characterized in that, described at least a Resins, epoxy is one or more compounds that are selected from down group: cycloaliphatic epoxides, cycloaliphatic epoxides with glycol modification, epoxy-Novolak resin, multifunctional (poly-epoxy) Resins, epoxy, dihydroxyphenyl propane basic ring epoxy resins, Bisphenol F basic ring epoxy resins, and composition thereof.
7. solidified resin system as claimed in claim 1 is characterized in that, it also comprises one or more following components: catalyzer, additional stiffening agent, toughner, flame-retardant additive, filler and non-Resins, epoxy.
8. method for preparing curable Resins, epoxy, it comprises and mixes following component:
(a) at least a Resins, epoxy of 35-65 weight %; With
(b) the diamino alcohol compound of 0.1-35 weight % with following formula:
Figure FSA00000410078600021
Wherein R is hydrogen, alkyl or aryl independently; R 1Be hydrogen or alkyl independently; Perhaps R and R 1Can be joined together to form cycloalkyl; R 2Be hydrogen, alkyl or aryl independently; R 3Be hydrogen, alkyl or aryl independently; R 4Be hydrogen or alkyl independently; Perhaps R 3And R 4Can be joined together to form cycloalkyl; Wherein all wt percentage ratio is benchmark in the gross weight of solidified resin system all.
9. method as claimed in claim 7 is characterized in that, the described curable second-order transition temperature of resin system after solidifying is greater than 120 ℃.
10. method as claimed in claim 8 is characterized in that, described diamino alcohol compound is 2-nitropropane and the reduzate that is selected from a kind of aldehyde in crotonic aldehyde and the phenylacrolein.
11. method as claimed in claim 8 is characterized in that, wherein R, R 1, R 3And R 4Each is alkyl naturally, R 2Be methyl or phenyl, the described curable second-order transition temperature of resin system after solidifying is greater than 120 ℃.
12. method as claimed in claim 8, it is characterized in that, described at least a Resins, epoxy is one or more compounds that are selected from down group: cycloaliphatic epoxides, cycloaliphatic epoxides with glycol modification, epoxy-Novolak resin, multifunctional (poly-epoxy) Resins, epoxy, dihydroxyphenyl propane basic ring epoxy resins, Bisphenol F basic ring epoxy resins, and composition thereof.
CN201010618068.8A 2009-12-22 2010-12-21 Novel diamino-alcohol compounds, their manufacture and use in epoxy resins Active CN102181044B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US28463709P 2009-12-22 2009-12-22
US61/284,637 2009-12-22

Publications (2)

Publication Number Publication Date
CN102181044A true CN102181044A (en) 2011-09-14
CN102181044B CN102181044B (en) 2013-07-10

Family

ID=43844552

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201010618068.8A Active CN102181044B (en) 2009-12-22 2010-12-21 Novel diamino-alcohol compounds, their manufacture and use in epoxy resins

Country Status (6)

Country Link
US (1) US8524857B2 (en)
EP (1) EP2341093B1 (en)
CN (1) CN102181044B (en)
BR (1) BRPI1005890A8 (en)
CA (1) CA2723359C (en)
MX (1) MX2010013996A (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2723493C (en) * 2009-12-22 2013-08-06 Dow Global Technologies, Inc. Novel diamino-alcohol compounds, their manufacture and use in high solids mineral slurries
EP2931781B1 (en) * 2012-12-14 2020-11-04 Blue Cube IP LLC Modified epoxy resins
US8933189B2 (en) 2013-03-15 2015-01-13 E I Du Pont De Nemours And Company Polymers derived from renewably resourced lysinol

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2475996A (en) * 1946-11-02 1949-07-12 Shell Dev Dinitro alcohols and process of producing the same from unsaturated aldehydes
US4293682A (en) * 1980-05-12 1981-10-06 Milliken Research Corporation Nitrogen containing compounds and compositions
US4340717A (en) * 1981-03-12 1982-07-20 Milliken Research Corporation Nitrogen-containing compounds
CN1798785A (en) * 2003-01-27 2006-07-05 分解性能产品有限责任公司 Epoxy resin curing compositions and resin compositions including same

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3607833A (en) 1969-10-03 1971-09-21 Vanderbilt Co R T Prepolymer of epoxy resin and tris(hydroxymethyl) aminomethane and curable composition thereof
US3943104A (en) 1973-03-09 1976-03-09 Jefferson Chemical Company, Inc. Method of accelerating epoxy curing
US4330644A (en) 1981-04-03 1982-05-18 Shell Oil Company Curable tris(hydroxyalkyl) aminomethane-modified epoxy resin composition
US5112926A (en) 1989-01-09 1992-05-12 Industrial Technology Research Institute Thermal-resistant resin composition for printed circuit boards based on triazine modified epoxy resin blends
US5436339A (en) * 1991-03-06 1995-07-25 Abbott Laboratories Process for the preparation of a substituted diaminoalcohol
US5478885A (en) 1994-04-15 1995-12-26 Shell Oil Company Composition of epoxy resin, epoxidized block polydiene and curing agent
US20070065669A1 (en) 2003-09-05 2007-03-22 Edmondson Stephen J Curable alkanolamine-containing epoxy powder coating composition
US8742018B2 (en) 2008-01-08 2014-06-03 Dow Global Technologies Llc High Tg epoxy systems for composite applications
US8070045B1 (en) * 2010-12-02 2011-12-06 Rohm And Haas Electronic Materials Llc Curable amine flux composition and method of soldering
US8070044B1 (en) * 2010-12-02 2011-12-06 Rohm And Haas Electronic Materials Llc Polyamine flux composition and method of soldering

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2475996A (en) * 1946-11-02 1949-07-12 Shell Dev Dinitro alcohols and process of producing the same from unsaturated aldehydes
US4293682A (en) * 1980-05-12 1981-10-06 Milliken Research Corporation Nitrogen containing compounds and compositions
US4340717A (en) * 1981-03-12 1982-07-20 Milliken Research Corporation Nitrogen-containing compounds
CN1798785A (en) * 2003-01-27 2006-07-05 分解性能产品有限责任公司 Epoxy resin curing compositions and resin compositions including same

Also Published As

Publication number Publication date
EP2341093A1 (en) 2011-07-06
US8524857B2 (en) 2013-09-03
CN102181044B (en) 2013-07-10
BRPI1005890A2 (en) 2013-04-02
US20110152407A1 (en) 2011-06-23
MX2010013996A (en) 2012-06-08
CA2723359A1 (en) 2011-06-22
BRPI1005890A8 (en) 2017-10-10
CA2723359C (en) 2015-03-17
EP2341093B1 (en) 2014-06-18

Similar Documents

Publication Publication Date Title
US9212287B2 (en) Low-emission hardener for epoxy resins
ES2702821T3 (en) Amina dilutable in water and its applications
ES2637367T3 (en) Curing agents of benzylated polyamine
AU2013372263B2 (en) Hardeners for low-emission epoxy resin products
JP6189851B2 (en) Curing agent for epoxy resin coating
US9290609B2 (en) Hardener for epoxy resins
JP2018532003A (en) Low emission epoxy resin composition
CN103819657A (en) Benzylated polyalkylene polyamines and uses thereof
AU2010330120A1 (en) Low-viscosity epoxy resin composition with low blushing
US20220298296A1 (en) Waterborne epoxy curing agent
JP7177580B2 (en) Epoxy resin curing agent, epoxy resin composition and cured product thereof
CN102181044B (en) Novel diamino-alcohol compounds, their manufacture and use in epoxy resins
JP3837134B2 (en) One-component heat-curable epoxide composition
EP3735434B1 (en) Curing agents for epoxy resins with low tendency to the formation of carbamates
JP4596123B2 (en) Low temperature curing type epoxy resin curing agent and epoxy resin composition
WO2022215494A1 (en) Epoxy resin curing agent, epoxy resin composition, and coating
JP2022114932A (en) Epoxy resin curative agent, epoxy resin composition, and coating
JP2004115427A (en) Modified cycloaliphatic polyamine

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
ASS Succession or assignment of patent right

Owner name: ANGUS CHEMICAL

Free format text: FORMER OWNER: DOW GLOBAL TECHNOLOGIES INC.

Effective date: 20150519

Free format text: FORMER OWNER: ANGUS CHEMICAL

Effective date: 20150519

C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20150519

Address after: Illinois State

Patentee after: Angus Chemical

Address before: Michigan

Patentee before: Dow Global Technologies Inc.

Patentee before: Angus Chemical